Cyclohexane derivatives

ABSTRACT

Various substituted cyclohexane-1,3-diones are useful as herbicides. 
     An exemplary species is 2-[1-(allyloxyamino)propylidene]-5,5-dimethylcyclohexane-1,3-dione.

This is a division of application Ser. No. 490,349 filed July 22, 1974 now U.S. Pat. No. 3,950,420.

DETAILED DESCRIPTION OF THE INVENTION

This invention relates to novel compounds of cyclohexane derivatives, to a process for the preparation thereof and their uses as selective herbicide.

In particularly this invention relates to new herbicidally active compositions and to method for killing undesired plants.

It has been found that outstanding herbicidal activity can be obtained by applying to the weed habitat, the compounds represented by the following formula: ##STR1## wherein R₁ is selected from the group consisting of hydrogen, alkyl and phenyl,

R₂ is selected from the group consisting of alkyl, straight or branched chain lower alkenyl, lower alkynyl, lower alkoxyalkyl, lower alkylthiomethyl, lower alkoxycarbonyl-alkyl and benzyl,

X is a same or different substituent which is selected from the group consisting of alkyl, lower alkoxycarbonyl, halogen, cyano, phenyl, phenyl substituted with halogen or methoxy, styryl, furyl, thienyl, 5,5-pentamethylene and 4,5-tetramethylene,

n is 0 or an integer from 1 to 6;

Or a hydrate or a metal salt of the compound defined herein above.

Preferred are those compounds represented by the following formula: ##STR2## wherein R₁ is ethyl or propyl group and R₂ is ethyl, propyl, allyl or propargyl group.

Particularly preferred because of their high order of herbicidal activity are:

2-[1-(ALLYLOXYAMINO)PROPYLIDENE]-5,5-DIMETHYLCYCLOHEXANE-1,3-DIONE

2-[1-(ALLYLOXYAMINO)BUTYLIDENE]-5,5-DIMETHYLCYCLOHEXANE-1,3-DIONE

2-[1-(PROPARGYLOXYAMINO)BUTYLIDENE]-5,5-DIMETHYLCYCLOHEXANE-1,3-DIONE

2-[1-(ETHOXYAMINO)PROPYLIDENE]-5-ISOPROPYLCYCLOHEXANE-1,3-DIONE

2-[1-(ALLYLOXYAMINO)PROPYLIDENE]-5-ISOPROPYLCYCLOHEXANE-1,3-DIONE

It is expected that the said compound represented by the above formula [ I] has the following three chemical formulae because of tautomerism:

An explanation of the drawing:

FIG. 1 is the infrared spectrum of 2-[1-(allyloxyamino)propylidene]-5,5-dimethylcyclohexane-1,3-dione

FIG. 2 is the infrared spectrum of 2-[1-(allyloxyamino)propylidene]-5,5-dimethylcyclohexane-1,3-dione hydrate

FIG. 3 is the infrared spectrum of 2-[1-(allyloxyamino)butylidene]-5,5-dimethylcyclohexane-1,3-dione

FIG. 4 is the infrared spectrum of 2-[1-(allyloxyamino)butylidene]-5,5-dimethylcyclohexane-1,3-dione hydrate

The compounds of this invention can be prepared in accordance with the following equation; ##STR4## wherein R₁, R₂, X and n are as previously defined.

The above reaction can be conducted in an inert solvent.

As an inert solvent, acetone, ether, methylalcohol, ethylalcohol, isopropylalcohol, benzene, tetrahydrofuran, chloroform, acetonitrile, dichloroethane, dichloromethane, ethyl acetate, dioxane, toluene, xylene and dimethyl sulfoxide etc. are used.

Reaction temperature is from -10° C to the boiling point of employed solvent, preferably from 10 to 60 and the reaction terminates between 0.5 and several hours.

After the reaction terminated, the employed solvent, if necessary, is replaced and then, the reaction mixture is extracted with an alkaline solution and further, an alkaline layer is acidified with hydrochloric acid, whereby the crude product is isolated from the reaction mixture by extraction with solvent or by filtration.

In case of crystalline substance, the crude product can be purified by recrystallization and in oily substance the crude product can be purified by distillation or isolation by column chromatography.

A chemical formula for the resulting purified compound can be confirmatively identified by means of an elementary analysis, NMR spectrum and IR spectrum.

When above formula [VI] represents 5,5-dimethyl-2-acyl-3-hydroxy-2-cyclohexene-1-one, above starting compound can be prepared in accordance with the following equation: ##STR5## wherein R₁ is as previously defined.

It is also expected that the starting compound represented by the formula [VI] has the same three chemical formulas as the formula [ I] because of tautomerism.

The sodium and potassium salts are prepared by treating a compound of formula [I] above with a sodium or potassium hydroxide in aqueous solution or an organic solvent such as acetone, methanol, ethanol or dimethylformamide. The salts are isolated by filtration or by evaporation of the resulting solution.

The calcium, barium, manganese, copper, zinc, nickel, cobalt, iron and silver salts are prepared from the sodium salt by treatment with the appropriate inorganic metal salt, e.q. calcium chloride, barium chloride, copper sulfate, zinc chloride, nickel chloride, and cobalt nitrate.

The calcium salt is also prepared by treating a compound of formula [I] above with calcium hydroxide.

Some metal salt of the present invention produced with above mentioned process may cause partially a chemical change or a decomposition at a high temperature, so that it does not show a clear melting point. Therefore, by applying infrared ray absorptive spectrum to the raw material and the reaction compound, a formation of the metal salt can be identified through a transference of absorption band and a change of absorption intensity. In the other words, the raw material compound having the said general formula [I] indicates an absorption of carbonyl group at a wavelength 1605cm⁻ ¹ and 1655cm⁻ ¹, whereas the corresponding metal salt shows the absorption at a side of longer wavelength. Further, in some occasion, an anion such as OH⁻ may be simultaneous coordinated with a metal atom of some metal salt obtained above.

Some of the compound of this invention may form hydrate thereof as follows: ##STR6## wherein R₁, R₂, X and n are as previously defined.

The hydrate of the compound of the invention also has superior herbicidal activity.

In order to facilitate a clear understanding of the invention, the following preferred specific embodiments are described as illustrative and not as limiting the invention.

EXAMPLE 1 Preparation of 2-[1-(ethoxyamino)ethylidene -5,5-dimethylcyclohexane-1,3-dione

1.8g (0.01 mol) of 2-acetyl-5,5-dimethyl-3-hydroxy-2-cyclohexene-1-one was dissolved in 10ml of ethanol and 0.6g (0.01 mol) of ethoxyamine was added to it and the resulting solution was stirred at a room temperature during 3 hours and then, the said ethanol was distilled off from it under a reduced pressure and a residual material was dissolved in chloroform.

The resulting chloroform solution was extracted for two times with aqueous solution containing 5 weight percent of sodium hydroxide and an alkaline layer produced thereto was acidified with hydrochloric acid and then an oily material separated thereto was extracted for two times with 10ml of chloroform.

A chloroform layer produced thereto was washed with water and it was dried and then, it was distilled off under a reduced pressure and thereby, the objective compound, as a colorless, oily material was obtained.

A yield amount: 2.1g (93 weight percent of yield rate)

A refractive index: n_(D).sup. 21.5 1.5094

EXAMPLE 2

The following compounds (C) can be synthesized by the method of Example 1 substituting the appropriate substituted 2-acyl-3-hydroxy-2-cyclohexene-1-one (A) for 2-acetyl-5,5-dimethyl-3-hydroxy-2-cyclohexene-1-one and the appropriate O-substituted hydroxyamine (B) for ethoxyamine.

Compound No. 31

A. 5,5-dimethyl-3-hydroxy-2-propyonyl-2-cyclohexene-1-one, 1.96g

B. ethoxyamine, 0.67g

C. 2-[1-(ethoxyamino)propylidene]-5,5-dimethylcyclohexane-1,3-dione,

yield amount: 2.3g (97 weight percent of yield rate)

refractive index: n_(D).sup. 24 1.5027

Compound No. 50

A. 5,5-dimethyl-3-hydroxy-2-propyonyl-2-cyclohexene-1-one, 3.92g

B. allyloxyamine, 1.6g

C. 2-[1-(allyloxyamino)propylidene]-5,5-dimethylcyclohexane-1,3-dione,

yield amount: 4.6g (92 weight percent of yield rate)

refractive index: n_(D) ²⁴ 1.5119

Compound No. 75

A. 2-butyryl-5,5-dimethyl-3-hydroxy-2-cyclohexene-1-one, 2.1g

B. ethoxyamine, 0.67g

C. 2-[1-(ethoxyamino)butylidene]-5,5-dimethylcyclohexane-1,3-dione,

yield amount: 2.1g (83 weight percent of yield rate)

refractive index: n_(D) ²¹ 1.4965

Compound No. 83

A. 2-butyryl-5,5-dimethyl-3-hydroxy-2-cyclohexene-1-one, 2.1g

B. allyloxyamine, 0.8g

C. 2-[1-(allyloxyamino)butylidene]-5,5-dimethylcyclohexane-1,3-dione,

yield amount: 2.2g (83 weight percent of yield rate)

refractive index: n_(D) ²¹ 1.5089

Compound No. 96

A. 2-butyryl-5,5-dimethyl-3-hydroxy-2-cyclohexene-1-one, 2.1g

B. hexyloxyamine, 1.29g

C. 2-[1-(hexyloxyamino)butylidene]-5,5-dimethylcyclohexane-1,3-dione,

yield amount: 2.5g (81 weight percent of yield rate)

refractive index: n_(D) ²⁵ 1.4725

EXAMPLE 3 2-[1-(allyloxyamino)ethylidene]-5,5-dimethylcyclohexane-1,3-dione

1.8g (0.01 mol) of 2-acetyl-5,5-dimethyl-3-hydroxy-2-cyclohexene-1-one was dissolved in 10ml of ethanol and then, 0.73g (0.01 mol) of allyloxyamine was added in it and the resulting solution was agitated at 50° C during one hour and then, the said ethanol was distilled off under a reduced pressure and a residual material was dissolved in chloroform.

The resulting chloroform solution was extracted for two times with 7ml of an aqueous solution containing 10 weight percent of caustic soda. An alkaline layer produced thereto was acidified with hydrochloric acid and a separated crystal was filtered and washed with water and then, it was dried. Then, the said crystal was recrystallized from n-hexane and thereby, the objective compound was obtained as a colorless crystal.

A yield amount: 2.2g (93 weight percent of yield rate)

A melting point: 30.5° to 31.5° C

EXAMPLE 4 Colbalt salt of 2-[1-(allyloxyamino)propylidene]-5,5-dimethylcyclohexane-1,3-dione

Two gram of 2-[1-(allyloxyamino)propylidene]-5,5-dimethylcyclohexane-1,3-dione were dissolved in 10ml of acteone, and to which 20ml of water containing 0.32g of sodium hydroxide were added. After stirring 10 minutes, 5ml of water containing 1.16g of cobalt nitrate [CO(NO₃)₂ .6H₂ O] were added dropwise to the mixture. After stirring well, the precipitate was filtrated, washed with water and ether and dried. Gray crystal having a decomposition point of 153°-154° C was obtained.

Yield amount: 2.2g (98 weight percent of yield rate).

EXAMPLE 5

The following compounds (C) can be synthesized by the method of Example 4 substituting the appropriate substituted cyclohexane-1,3-dione (A) for 2-[1-(allyloxyamino)propylidene]-5,5-dimethylcyclohexane-1,3-dione, the appropriate inorganic metal salt (B) for cobalt nitrate, and the appropriate amount of sodium hydroxide (D).

Compound No. 141

A. 2-[1-(allyloxyamino)butylidene]-5,5-dimethylcyclohexane-1,3-dione (2.1g)

B. nickel chloride NiCl₂ .6H₂ O (0.95g)

C. nickel salt of 2-[1-(allyloxyamino)butylidene]-5,5-dimethylcyclohexane-1,3-dione (2.2g), 94 weight percent of yield rate, decomposition point: over 250° C

D. sodium hydroxide (0.32g)

Compound No. 150

A. 2-[1-(benzyloxyamino)butylidene]-5,5-dimethylcyclohexane-1,3-dione (3.1g)

B. copper sulfate CuSO₄ .5H₂ O (1.25g)

C. copper salt of 2-[1-(benzyloxyamino)butylidene]-5,5-dimethylcyclohexane-1,3-dione (3.2g), 93 weight percent of yield rate, decomposition point: 126°-127° C

D. sodium hydroxide (0.4g)

Compound No. 112

A. 2-[1-(allyloxyamino)ethylidene]-5-phenylcyclohexane-1,3-dione (2.8g)

B. copper sulfate CuSO₄ .5H₂ O (0.125g)

C. copper salt of 2-[1-(allyloxyamino)ethylidene]-5-phenylcyclohexane-1,3 -dione (3g), 95 weight percent of yield rate, decomposition point: 188°-189° C

D. sodium hydroxide (0.4g)

EXAMPLE 6 Sodium salt of 2-[1-(allyloxyamino)butylidene]-5,5-dimethylcyclohexane-1,3-dione

2.6g of 2-[1-(allyloxyamino)butylidene]-5,5-dimethylcyclohexane-1,3-dione was dissolved in 20ml of acetone. 0.4g of sodium hydroxide dissolved in 5ml of water was added to the solution. The solvent was evaporated at reduced pressure after stirring 10 minutes. White crystal having a melting point of 80° to 82° C was obtained by crystallizing the glass-state substance from the mixture of ethanol and benzene.

Yield amount: 2.6g (91 weight percent of rate)

EXAMPLE 7 Calcium salt of 2-[1-(allyloxyamino)propylidene]-5,5-dimethylcyclohexane-1,3-dione

2.5g of 2-[1-(allyloxyamino)propylidene]-5,5-dimethylcyclohexane-1,3-dione was dissolved in 20ml of ethanol. 0.37g of calcium hydroxide dissolved in 20ml of water was added little by little to the solution under stirring. After stirring 1 hr. the insoluble substance was filtrated. The filtrate was evaporated at reduced pressure and precipitated white crystal was washed and dried.

Yield amount; 2.7g (100 weight percent of yield rate)

Decomposition point; 107° - 108° C

EXAMPLE 8 2-[1-(allyloxyamino)butylidene]-5,5-dimethylcyclohexane-1,3-dione hydrate

2.65g of 2-[1-(allyloxyamino)butylidene]-5,5-dimethylcyclohexane-1,3-dione was added to 10ml of water and the mixture was vigorously stirred. After several minutes, the precipitate was filtered, washed with water and dried. White crystal having a melting point of 46°-47° C was obtained.

Yield amount: 2.8g (100 weight percent of yield rate)

EXAMPLE 9

The following hydrate compounds (B) can be obtained by the method of Example 8 substituting the appropriate substituted cyclohexane-1,3-dione (A) for 2-[1-(allyloxyamino)butylidene]-5,5-dimethylcyclohexane-1,3-dione.

Compound No. 154

A. 2-[1-(allyloxyamino)propylidene]-5-methylcyclohexane-1,3-dione (2.37g)

B. 2-[1-(allyloxyamino)propylidene]-5-methylcyclohexane-1,3-dione hydrate (2.5g)

Yield rate: 100 weight percent, m.p.: 46° - 48° C.

Compound No. 156

A. 2-[1-(ethoxyamino)propylidene]-5-phenylcyclohexane-1,3-dione (2.87 g)

B. 2-[1-(ethoxyamino)propylidene]-5-phenylcyclohexane-1,3-dione hydrate (3.0g)

Yield rate: 100 weight percent, m.p.: 67°-68° C.

In addition to the above mentioned compounds described in the preceding example, some typical compounds of the present invention are listed in Table 1.

                                      Table 1                                      __________________________________________________________________________     Compd. No.                                                                                Chemical Name     Physical Constant                                 __________________________________________________________________________     1      2-[1-(allyloxyamino)methylidene]-5,5-                                                                m.p. 55 - 60° C                                   dimethylcyclohexane-1,3-dione                                           2      2-[1-(ethoxyamino)ethylidene]-cyclo-                                                                 m.p. 48 - 50° C                                   hexane-1,3-dione                                                        3      2-[1-(ethoxyamino)ethylidene]-4-cyano-                                                               n.sub.D.sup.23.5 1.5280                                  5,5-dimethylcyclohexane-1,3-dione                                       4      2-[1-(ethoxyamino)ethylidene]-4-iso-                                                                 n.sub.D.sup.24 1.5115                                    propylcyclohexane-1,3-dione                                             5      2-[1-(ethoxyamino)ethylidene]-4-                                                                     n.sub.D.sup.22.5 1.5047                                  ethoxycarbonyl-4-ethylcyclohexane-                                             1,3-dione                                                               6      2-[1-(ethoxyamino)ethylidene]-4-bromo-                                                               n.sub.D.sup.23 1.5405                                    5,5-dimethylcyclohexane-1,3-dione                                       7      2-[1-(ethoxyamino)ethylidene]-4-                                                                     n.sub.D.sup.21 1.5050                                    ethoxycarbonyl-5,5-dimethylcyclo-                                              hexane-1,3-dione                                                        8      2-[1-(ethoxyamino)ethylidene]-5-                                                                     n.sub.D.sup.24 1.5132                                    ethylcyclohexane-1,3-dione                                              9      2-[1-(ethoxyamino)ethylidene]-4-                                                                     n.sub.D.sup.25 1.5065                                    methoxycarbonyl-5,5-dimethylcyclo-                                             hexane-1,3-dione                                                        10     2-[1-(ethoxyamino)ethylidene]-5,5-                                                                   n.sub.D.sup.21.5 1.5094                                  dimethylcyclohexane-1,3-dione                                           11     2-[1-(ethoxyamino)ethylidene]-5-                                                                     m.p. 56 - 57° C                                   phenylcyclohexane-1,3-dione                                             12     2-[1-(allyloxyamino)ethylidene)]-                                                                    m.p. 55 - 57° C                                   cyclohexane-1,3-dione                                                   13     2-[1-(allyloxyamino)ethylidene]-4-                                                                   n.sub.D.sup.32 1.5468                                    bromo-5,5-dimethylcyclohexane-1,3-                                             dione                                                                   14     2-[1-(allyloxyamino)ethylidene]-4-                                                                   m.p. 78 - 80° C                                   cyano-5,5-dimethylcyclohexane-1,3-                                             dione                                                                   15     2-[1-(allyloxyamino)ethylidene]-4-                                                                   n.sub.D.sup.21 1.5128                                    ethoxycarbonyl-5,5-dimethylcyclo-                                              hexane-1,3-dione                                                        16     2-[1-(allyloxyamino)ethylidene]-4-                                                                   n.sub. D.sup.25 1.5095                                   methoxycarbonyl-5,5-dimethylcyclo-                                             hexane-1,3-dione                                                        17     2-[1-(allyloxyamino)ethylidene]-5-                                                                   n.sub.D.sup.26 1.5203                                    ethylcyclohexane-1,3-dione                                              18     2-[1-(allyloxyamino)ethylidene]-5,5-                                                                 m.p. 30.5 - 31.5° C                               dimethylcyclohexane-1,3-dione                                           19     2-[1-(allyloxyamino)ethylidene]-5-                                                                   m.p. 34 - 35° C                                   phenylcyclohexane-1,3-dione                                             20     2-[1-(propoxyamino)ethylidene]-5,5-                                                                  n.sub.D.sup.18.5 1.5088                                  dimethylcyclohexane-1,3-dione                                           21     2-[1-(ethoxyamino)propylidene]-                                                                      n.sub.D.sup.24.5 1.5188                                  cyclohexane-1,3-dione                                                   22     2-[1-(ethoxyamino)propylidene]-5-                                                                    m.p. 65 - 66° C                                   (4-methylphenyl)cyclohexane-1,3-dione                                   23     2-[1-(ethoxyamino)propylidene]-5-(3-                                                                 m.p. 44 - 45° C                                   chlorophenyl)cyclohexane-1,3-dione                                      24     2-[1-(ethoxyamino)propylidene]-5-(4-                                                                 m.p. 59 - 60° C                                   methoxyphenyl)cyclohexane-1,3-dione                                     25     2-[1-(ethoxyamino)propylidene]-5-(4-                                                                 m.p. 92 - 93° C                                   chlorophenyl)cyclohexane-1,3-dione                                      26     2-[1-(ethoxyamino)propylidene]-5-                                                                    m.p. 67 - 68° C                                   phenylcyclohexane-1,3-dione                                             27     2-[1-(ethoxyamino)propylidene]-5-                                                                    m.p. 92 - 96° C                                   styrylcyclohexane-1,3-dione                                             28     2-[1-(ethoxyamino)propylidene]-5-(2-                                                                 m.p. 50 - 52° C                                   furyl)cyclohexane-1,3-dione                                             29     2-[1-(ethoxyamino)propylidene]-5-(2-                                                                 m.p. 68 - 69° C                                   thienyl)cyclohexane-1,3-dione                                           30     2-[1-(ethoxyamino)propylidene]-5-                                                                    n.sub.D.sup.20 1.5045                                    methylcyclohexane-1,3-dione                                             31     2-[1-(ethoxyamino) ropylidene]-5,5-                                                                  n.sub.D.sup.24 1.5027                                    dimethylcyclohexane-1,3-dione                                           32     2-[1-(ethoxyamino)propylidene]-5-iso-                                                                n.sub.D.sup.18 1.5111                                    propylcyclohexane-1,3-dione                                             33     2-[ 1-(ethoxyamino)propylidene]-5-                                                                   n.sub.D.sup.18.5 1.5019                                  hexylcyclohexane-1,3-dione                                              34     2-[1-(ethoxyamino)propylidene]-4-                                                                    n.sub.D.sup.21 1.5081                                    methyl-5,5-dimethylcyclohexane-1,3-                                            dione                                                                   35     2-[1-(ethoxyamino)propylidene]-4,4-                                                                  n.sub.D.sup.18 1.4946                                    dimethylcyclohexane-1,3-dione                                           36     2-[1-(ethoxyamino)propylidene]-4-                                                                    m.p. 47 - 48° C                                   cyano-5,5-dimethylcyclohexane-1,3-                                             dione                                                                   37     2-[ 1-(ethoxyamino)propylidene]-4-                                                                   n.sub.D.sup.24 1.5070                                    methoxycarbonyl-5,5-dimethylcyclo-                                             hexane-1,3-dione                                                        38     2-[1-(ethoxyamino)propylidene]-4-                                                                    n.sub.D.sup.16 1.5040                                    ethoxycarbonyl-5,5-dimethylcyclo-                                              hexane-1,3-dione                                                        39     2-[1-(ethoxyamino)propylidene]-4-n-                                                                  n.sub.D.sup.25 1.5078                                    propylcyclohexane-1,3-dione                                             40     2-[1-(ethoxyamino)propylidene]-4-iso-                                                                n.sub.D.sup.27 1.5055                                    butylcyclohexane-1,3-dione                                              41     2-[1-(methoxymethoxyamino)propylidene]-                                                              n.sub.D.sup.27 1.5017                                    5,5-dimethylcyclohexane-1,3-dione                                       42     2-[1-(buthoxymethoxyamino)propyli-                                                                   n.sub.D.sup.27 1.4927                                    dene]-5,5-dimethylcyclohexane-1,3-                                             dione                                                                   43     2-[1-(methylthiomethoxyamino)propyli-                                                                n.sub.D.sup.27 1.5582                                    dene]-5,5-dimethylcyclohexane-1,3-                                             dione                                                                   44     2-[1-(methylthiomethoxyamino)propyli-                                                                n.sub.D.sup.27 1.5328                                    dene]-5-isopropylcyclohexane-1,3-dione                                  45     2-[1-(methoxyethoxyamino)propylidene]-                                                               n.sub.D.sup.20 1.5100                                    5,5-dimethylcyclohexane-1,3-dione                                       46     2-[1-(ethoxycarbonylmethoxyamino)pro-                                                                n.sub.D.sup.20 1.5019                                    pylidene]-4,4-dimethylcyclohexane-1,3-                                         dione                                                                   47     2-[1-(propoxyamino)propylidene]-5,5-                                                                 n.sub.D.sup.20 1.4994                                    dimethylcyclohexane-1,3-dione                                           48     2-[1-(allyloxyamino)propylidene]-                                                                    n.sub.D.sup.25 1.5265                                    cyclohexane-1,3-dione                                                   49     2-[1-(allyloxyamino)propylidene]-5-                                                                  n.sub.D.sup.20.5 1.5200                                  methylcyclohexane-1,3-dione                                             50     2-[1-(allyloxyamino)propylidene]-5,5-                                                                n.sub.D.sup.24 1.5119                                    dimethylcyclohexane-1,3-dione                                           51     2-[1-(allyloxyamino)propylidene]  -5-                                                                n.sub.D.sup.23.5 1.5140                                  isopropylcyclohexane-1,3-dione                                          52     2-[1-(allyloxyamino)propylidene]-5-                                                                  n.sub.D.sup.18.5 1.5082                                  hexylcyclohexane-1,3-dione                                              53     2-[1-(allyloxyamino)propylidene]-5-                                                                  n.sub.D.sup.22 1.5452                                    (2-furyl)cyclohexane-1,3-dione                                          54     2-[1-(allyloxyamino)propylidene]-5-                                                                  m.p. 48 - 50° C                                   phenylcyclohexane-1,3-dione                                             55     2-[1-(allyloxyamino)propylidene]-5-                                                                  n.sub.D.sup.21 1.5851                                    styrylcyclohexane-1,3-dione                                             56     2-[1-(allyloxyamino)propylidene]-4-                                                                  n.sub.D.sup.27 1.5338                                    bromo-6,6-dimethylcyclohexane-1,3-                                             dione                                                                   57     2-[1-(allyloxyamino)propylidene]-4-                                                                  n.sub.D.sup.26 1.5365                                    bromo-5,5-dimethylcyclohexane-1,3-                                             dione                                                                   58     2-[1-(allyloxyamino)propylidene]-4-                                                                  m.p. 62 - 63° C                                   cyano-5,5-dimethylcyclohexane-1,3-                                             dione                                                                   59     2-[1-(allyloxyamino)propylidene]-4-                                                                  n.sub.D.sup.24.5 1.5088                                  methoxycarbonyl-5,5-dimethylcyclo-                                             hexane-1,3-dione                                                        60     2-[1-(allyloxyamino)propylidene]-4-                                                                  n.sub.D.sup.20 1.5146                                    ethoxycarbonyl-5-methylcyclohexane-                                            1,3-dione                                                               61     2-[1-(allyloxyamino)propylidene]-4-                                                                  n.sub.D.sup.18 1.5079                                    ethoxycarbonyl-5,5-dimethylcyclo-                                              hexane-1,3-dione                                                        62     2-[1-(allyloxyamino)propylidene]-4-                                                                  n.sub.D.sup.22 1.5078                                    ethoxycarbonyl-4-ethylcyclohexane-1,3-                                         dione                                                                   63     2-[1-(allyloxyamino)propylidene]-4-                                                                  n.sub.D.sup.21 1.5138                                    methyl-5,5-dimethylcyclohexane-1,3-                                            dione                                                                   64     2-[1-(allyloxyamino)propylidene]-4,4-                                                                n.sub.D.sup.18 1.5138                                    dimethylcyclohexane-1,3-dione                                           65     2-[1-(allyloxyamino)propylidene]-4-                                                                  n.sub.D.sup.20 1.5152                                    isopropylcyclohexane-1,3-dione                                          66     2-[1-(allyloxyamino)propylidene]-4-n-                                                                n.sub.D.sup.25 1.5103                                    propylcyclohexane-1,3-dione                                             67     2-[1-(allyloxyamino)propylidene]-4-n-                                                                n.sub.D.sup.21.5 1.5134                                  butylcyclohexane-1,3-dione                                              68     2-[1-(allyloxyamino)propylidene]-4-                                                                  n.sub.D.sup.25 1.5091                                    n-pentylcyclohexane-1,3-dione                                           69     2-[1-(propargyloxyamino)propylidene]-                                                                n.sub.D.sup.18.5 1.5218                                  5,5-dimethylcyclohexane-1,3-dione                                       70     2-[1-(methallyloxyamino)propylidene]-                                                                n.sub.D.sup.23 1.5107                                    5,5-dimethylcyclohexane-1,3-dione                                       71     2-[1-(n-butoxyamino)propylidene]-5,5-                                                                n.sub.D.sup.18.5 1.5027                                  dimethylcyclohexane-1,3-dione                                           72     2-[1-(isobutoxyamino)propylidene]-                                                                   n.sub.D.sup.23 1.4976                                    5,5-dimethylcyclohexane-1,3-dione                                       73     2-[1-(benzyloxyamino)propylidene]-5,5-                                                               m.p. 58 - 59° C                                   dimethylcyclohexane-1,3-dione                                           74     2-[1-(methoxyamino)butylidene]-5,5-                                                                  n.sub.D.sup.23 1.4940                                    dimethylcyclohexane-1,3-dione                                           75     2-[1-(ethoxyamino)butylidene]-5,5-                                                                   n.sub.D.sup.21 1.4965                                    dimethylcyclohexane-1,3-dione                                           76     2-[1-(ethoxyamino)butylidene]-5-                                                                     n.sub.D.sup.18 1.5068                                    isopropylcyclohexane-1,3-dione                                          77     2-[1-(ethoxyamino)butylidene]-5-                                                                     n.sub.D.sup.18.5 1.5005                                  hexylcyclohexane-1,3-dione                                              78     2-[1-(ethoxyamino)butylidene]-4-                                                                     m.p. 83 - 87° C                                   cyano-5,5-dimethylcyclohexane-1,3-                                             dione                                                                   79     2-[1-(ethoxyamino)butylidene]-4-                                                                     n.sub.D.sup.24.5 1.5007                                  methoxycarbonyl-5,5-dimethyl-                                                  cyclohexane-1,3-dione                                                   80     2-[1-(ethoxyamino)butylidene]-4-                                                                     n.sub.D.sup.21.5 1.4990                                  ethoxycarbonyl-5,5-dimethylcyclo-                                              hexane-1,3-dione                                                        81     2-[1-(ethoxyamino)butylidene]-4,4-                                                                   n.sub.D.sup.20 1.5050                                    dimethylcyclohexane-1,3-dione                                           82     2-[1-(isopropoxyamino)butylidene]-                                                                   n.sub.D.sup.33 1.4939                                    5,5-dimethylcyclohexane-1,3-dione                                       83     2-[1-(allyloxyamino)butylidene]-5,5-                                                                 n.sub.D.sup.21 1.5089                                    dimethylcyclohexane-1,3-dione                                           84     2-[1-(allyloxyamino)butylidene]-5-                                                                   n.sub.D.sup.16 1.5135                                    isopropylcyclohexane-1,3-dione                                          85     2-[1-(allyloxyamino)butylidene]-5-                                                                   n.sub.D.sup.18.5 1.5051                                  hexylcyclohexane-1,3-dione                                              86     2-[1-(allyloxyamino)butylidene]-5-                                                                   m.p. 52 - 53° C                                   (4-methoxyphenyl)cyclohexane-1,3-dione                                  87     2-[1-(allyloxyamino)butylidene]-5-                                                                   n.sub.D.sup.25.5 1.5657                                  (3-chlorophenyl)cyclohexane-1,3-dione                                   88     2-[1-(allyloxyamino)butylidene]-5-                                                                   m.p. 36 - 37° C                                   (4-chlorophenyl)cyclohexane-1,3-dione                                   89     2-[1-(allyloxyamino)butylidene]-4-                                                                   m.p. 105 - 108° C                                 cyano-5,5-dimethylcyclohexane-1,3-                                             dione                                                                   90     2-[1-(allyloxyamino)butylidene]-4-                                                                   n.sub.D.sup.24.5 1.5063                                  methoxycarbonyl-5,5-dimethylcyclo-                                             hexane-1,3-dione                                                        91     2-[1-(allyloxyamino)butylidene]-4-                                                                   n.sub.D.sup.21 1.5066                                    ethoxycarbonyl-5,5-dimethylcyclo-                                              hexane-1,3-dione                                                        92     2-[1-(allyloxyamino)butylidene]-4-                                                                   n.sub.D.sup.22.5 1.5078                                  ethoxycarbonyl-4-ethylcyclohexane-                                             1,3-dione                                                               93     2-[1-(allyloxyamino)butylidene]-4,4-                                                                 n.sub.D.sup.18 1.4753                                    dimethylcyclohexane-1,3-dione                                           94     2-[1-(allyloxyamino)butylidene]-4-                                                                   n.sub.D.sup.23.5 1.5058                                  isopropylcyclohexane-1,3-dione                                          95     2-[1-(propargyloxyamino)butylidene]-                                                                 n.sub.D.sup.31 1.5132                                    5,5-dimethylcyclohexane-1,3-dione                                       96     2-[1-(hexyloxyamino)butylidene]-5,5-                                                                 n.sub.D.sup.25 1.4725                                    dimethylcyclohexane-1,3-dione                                           97     2-[1-(ethoxyamino)isobutylidene]-                                                                    n.sub.D.sup.23 1.5013                                    5,5-dimethylcyclohexane-1,3-dione                                       98     2-[1-(ethoxyamino)hexylidene]-5,5-                                                                   n.sub.D.sup.31 1.4881                                    dimethylcyclohexane-1,3-dione                                           99     2-[1-(allyloxyamino)hexylidene]-5,5-                                                                 n.sub.D.sup.31 1.5040                                    dimethylcyclohexane-1,3-dione                                           100    2-[1-(ethoxyamino)benzylidene]-5,5-                                                                  m.p. 150 - 151° C                                 dimethylcyclohexane-1,3-dione                                           101    2-[1-(allyloxyamino)benzylidene]-5,5-                                                                m.p. 169 - 170° C                                 dimethylcyclohexane-1,3-dione                                           102    2-[1-(ethoxyamino)propylidene]-5,5-                                                                  n.sub.D.sup.21 1.5272                                    pentamethylenecyclohexane-1,3-dione                                     103    2-[1-(allyloxyamino)propylidene]-5,5-                                                                n.sub.D.sup.21 1.5336                                    pentamethylenecyclohexane-1,3-dione                                     104    2-[1-(ethoxyamino)propylidene]-4,5-                                                                  n.sub.D.sup.21 1.5282                                    tetramethylenecyclohexane-1,3-dione                                     105    2-[1-(allyloxyamino)propylidene]-4,5-                                                                n.sub.D.sup.21 1.5347                                    tetramethylenecyclohexane-1,3-dione                                     106    Manganese salt of 2-[1-(ethoxyamino)-                                                                m.p. 225 - 226° C(d.)                             ethylidene]-5,5-dimethylcyclohexane-                                           1,3-dione                                                               107    Potassium salt of 2-[1-(ethoxyamino)-                                                                m.p. 110 - 112° C(d.)                             ethylidene]-5,5-dimethylcyclohexane-                                           1,3-dione                                                               108    Copper salt of 2-[1-(ethoxyamino)-                                                                   m.p. 156 - 157° C(d.)                             ethylidene]-5,5-dimethylcyclohexane-                                           1,3-dione                                                               109    Copper salt of 2-[1-(ethoxyamino)-                                                                   m.p. 161 - 164° C(d.)                             ethylidene]-4-cyano-5,5-dimethylcyclo-                                         hexane-1,3-dione                                                        110    Sodium salt of 2-[1-(ethoxyamono)-                                                                   m.p. 110 - 120° C(d.)                             ethylidene]-4-methoxycarbonyl-5,5-                                             dimethylcyclohexane-1,3-dione                                           111    Copper salt of 2-[1-(allyloxyamino)-                                                                 m.p. 164 - 165° C(d.)                             ethylidene]-5-ethylcyclohexane-1,3-                                            dione                                                                   112    Copper salt of 2-[1-(allyloxyamino)-                                                                 m.p. 188 - 189° C(d.)                             ethylidene]-5-phenylcyclohexane-1,3-                                           dione                                                                   113    Copper salt of 2-[1-(allyloxyamino)                                                                  m.p. 154 - 158° C(d.)                             ethylidene]-4-cyano-5,5-dimethylcyclo-                                         hexane-1,3-dione                                                        114    Sodium salt of 2-[1-(allyloxyamino)-                                                                 m.p. 193 - 194° C(d.)                             ethylidene]-4-methoxycarbonyl-5,5-                                             dimethylcyclohexane-1,3-dione                                           115    Sodium salt of 2-[1-(allyloxyamino)-                                                                 m.p. 110 - 120° C(d.)                             ethylidene]-4-ethoxycarbonyl-5,5-                                              dimethylcyclohexane-1,3-dione                                           116    Copper salt of 2-[1-(methylthio-                                                                     m.p. 110° C(d.)                                   methoxyamino)propylidene]-5,5-                                                 dimethylcyclohexane-1,3-dione                                           117    Copper salt of 2-[1-(ethoxyamino)-                                                                   m.p. 197 - 198° C(d.)                             propylidene] -5-(2-furyl)cyclohexane-                                          1,3-dione                                                               118    Copper salt of 2-[1-(ethoxyamino)-                                                                   m.p. 184 - 185° C(d.)                             propylidene]-5-(2-thienyl)cyclohexane-                                         1,3-dione                                                               119    Copper salt of 2-[1-(ethoxyamino)-                                                                   m.p. 186 - 188° C(d.)                             propylidene]-5-(4-chlorophenyl)-                                               cyclohexane-1,3-dione                                                   120    Copper salt of 2-[1-(ethoxyamino)-                                                                   m.p. 184 - 185° C(d.)                             propylidene]-5-(3-chlorophenyl)-                                               cyclohexane-1,3-dione                                                   121    Copper salt of 2-[1-(ethoxyamino)-                                                                   m.p. 183 - 184° C(d.)                             propylidene]-5-(4-methylphenyl)-                                               cyclohexane-1,3-dione                                                   122    Copper salt of 2-[1-(ethoxyamino)-                                                                   m.p. 81 - 83° C(d.)                               propylidene]-4-cyano-5,5-dimethyl-                                             cyclohexane-1,3-dione                                                   123    Sodium salt of 2-[1-(ethoxyamino)-                                                                   m.p. 188 - 190° C(d.)                             propylidene]-4-ethoxycarbonyl-5,5-                                             dimethylcyclohexane-1,3-dione                                           124    Copper salt of 2-[1-(allyloxyamino)-                                                                 m.p. 146 - 147° C(d.)                             propylidene]-cyclohexane-1,3-dione                                      125    Copper salt of 2-[1-(allyloxyamino)-                                                                 m.p. 129 - 130° C(d.)                             propylidene]-5-methylcyclohexane-                                              1,3-dione                                                               126    Nickel salt of 2-[1-(allyloxyamino)-                                                                 m.p. 169 - 170° C(d.)                             propylidene]-5,5-dimethylcyclohexane-                                          1,3-dione                                                               127    Calcium salt of 2-[1-(allyloxyamino)-                                                                m.p. 107 - 108° C(d.)                             propylidene]-5,5-dimethylcyclohexane-                                          1,3-dione                                                               128    Cobalt salt of 2-[1-(allyloxyamino)-                                                                 m.p. 151 - 152° C(d.)                             propylidene]-5,5-dimethylcyclohexane-                                          1,3-dione                                                               129    Copper salt of 2-[1-(allyloxyamino)-                                                                 m.p. 145 - 146°  C(d.)                            propylidene]-5-isopropylcyclohexane-                                           1,3-dione                                                               130    Copper salt of 2-[1-(allyloxyamino)-                                                                 m.p. 78 - 80° C(d.)                               propylidene]-4-cyano-5,5-dimethyl-                                             cyclohexane-1,3-dione                                                   131    Sodium salt of 2-[1-(allyloxyamino-                                                                  m.p. 175 - 178° C(d.)                             propylidene]-4-methoxycarbonyl-5,5-                                            dimethylcyclohexane-1,3-dione                                           132    Sodium salt of 2-[1-(allyloxyamino)-                                                                 m.p. 110 - 120° C(d.)                             propylidene]-4-ethoxycarbonyl-5,5-                                             dimethylcyclohexane-1,3-dione                                           133    Calcium salt of 2-[1-(allyloxyamino)-                                                                m.p. 150 - 152° C(d.)                             propylidene]-4-propylcyclohexane-                                              1,3-dione                                                               134    Copper salt of 2-[1-(propargyloxy-                                                                   m.p. 126 - 127° C(d.)                             amino)propylidene]-5,5-dimethylcyclo-                                          hexane-1,3-dione                                                        135    Barium salt of 2-[1-(propoxyamino)-                                                                  m.p. 75 - 78° C(d.)                               propylidene]-5,5-dimethylcyclohexane-                                          1,3-dione                                                               136    Calcium salt of 2-[1-(isobutoxyamino)-                                                               m.p. 195 - 200° C(d.)                             propylidene]-5,5-dimethylcyclohexane-                                          1,3-dione                                                               137    Copper salt of 2-[1-(butoxyamino)-                                                                   m.p. 123 - 125° C(d.)                             propylidene)-5,5-dimethylcyclohexane-                                          1,3-dione                                                               138    Calcium salt of 2-[1-(ethoxyamino)-                                                                  m.p. 180° C(d.)                                   butylidene]-5,5-dimethylcyclohexane-                                           1,3-dione                                                               139    Copper salt of 2-[1-(ethoxyamino)-                                                                   m.p. 98 - 101° C(d.)                              butylidene]-4-cyano-5,5-dimethyl-                                              cyclohexane-1,3-dione                                                   140    Sodium salt of 2-[1-(ethoxyamino)-                                                                   m.p. 183 - 185° C(d.)                             butylidene]-4-methoxycarbonyl-5,5-                                             dimethylcyclohexane-1,3-dione                                           141    Nickel salt of 2-[1-(allyloxyamino)-                                                                 >m.p. 250°  C(d.)                                 butylidene]-5,5-dimethylcyclohexane-                                           1,3-dione                                                               142    Cobalt salt of 2-[1-(allyloxyamino)-                                                                 m.p. 153 - 154° C(d.)                             butylidene]-5,5-dimethylcyclohexane-                                           1,3-dione                                                               143    Sodium salt of 2-[1-(allyloxyamino)-                                                                 m.p. 80 - 82° C                                   butylidene]-5,5-dimethylcyclohexane-                                           1,3-dione                                                               144    Copper salt of 2-[1-(allyloxyamino)-                                                                 m.p. 145 - 146° C(d.)                             butylidene]-5-isopropylcyclohexane-                                            1,3-dione                                                               145    Copper salt of 2-[1-(allyloxyamino)-                                                                 m.p. 105 - 106° C(d.)                             butylidene]-5-hexcylcyclohexane-1,3-                                           dione                                                                   146    Copper salt of 2-[1-(allyloxyamino)-                                                                 m.p. 182 - 183° C(d.)                             butylidene]-5-(4-methoxyphenyl)cyclo-                                          hexane-1,3-dione                                                        147    Copper salt of 2-[1-(allyloxyamino)-                                                                 m.p. 92 - 95° C(d.)                               butylidene]-4-cyano-5,5-dimethyl-                                              cyclohexane-1,3-dione                                                   148    Sodium salt of 2-[1-(allyloxyamino)-                                                                 m.p. 192° C(d.)                                   butylidene]-4-methoxycarbonyl-5,5-                                             dimethylcyclohexane-1,3-dione                                           149    Sodium salt of 2-[1-(allyloxyamino)-                                                                 m.p. 110 - 120° C(d.)                             butylidene]-4-ethoxycarbonyl-5,5-                                              dimethylcyclohexane-1,3-dione                                           150    Copper salt m.p. 126 2-[1-(benzyloxyamino)-                                                          m.p. 126 - 127° C(d.)                             butylidene]-5,5-dimethylcyclohexane-                                           1,3-dione                                                               151    Copper salt of 2-[1-(allyloxyamino)-                                                                 m.p. 178 - 179° C(d.)                             propylidene]-4,5-tetramethylenecyclo-                                          hexane-1,3-dione                                                        152    2-[1-(allyloxyamino)butylidene]-5,5-                                                                 m.p. 47 - 49° C                                   dimethylcyclohexane-1,3-dione hydrate                                   153    2-[1-(allyloxyamino)propylidene]-5,5-                                                                m.p. 52 - 54° C                                   dimethylcyclohexane-1,3-dione hydrate                                   154    2-[1-(allyloxyamino)propylidene]-5-                                                                  m.p. 46 - 48° C                                   methylcyclohexane-1,3-dione hydrate                                     155    2-[1-(allyloxyamino)propylidene]-5-                                                                  m.p. 48 - 50° C                                   phenylcyclohexane-1,3-dione hydrate                                     156    2-[1-(ethoxyamino)propylidene]-5-                                                                    m.p. 67 - 68° C                                   phenylcyclohexane-1,3-dione hydrate                                     157    2-[1-(allyloxyamino)propylidene]-5,5-                                          diethylcyclohexane-1,3-dione                                            __________________________________________________________________________      *m.p. : melting point                                                          n.sub.D : refractive index                                                     d. : decomposition                                                       

Hereinafter, the compounds of this invention are represented by Compound No. in Table 1.

As mentioned previously, it has been found that the compounds of the invention possess superior herbicidal activity. The paragraphs which follow described in more detail the utility of this invention.

The compounds of the invention are particularly effective in the control of grass weeds such as annual bluegrass (Poa annua), water foxtail (Alopecurus aequalis), large crabgrass (Digitaria adscendens), green foxtail (Panicum viride L), wild oat (Avena fatua L) etc. and they hardly injure broad leaf crops such as adzuki bean (Phaseolus angularis) and soy bean (Glycine max) and sugar beets which easily suffer phyto-toxicity. Namely, the compounds of the invention are the selective herbicide.

It is already known that 4-hydroxy-6-methyl-α-pyrone derivatives has herbicidal properties as shown in Japanese Patent Publication No. 16916/1971.

But in order to destroy completely the said grass weeds, a large amount of the above herbicidal chemical is required and this is one drawback for above mentioned herbicidal compound.

In the other words, according to the descriptions of above mentioned prior art and the results of the later additional experiments by the inventors, a chemical amount containing 500g of effective ingredient, in proportion to 10 are ("are" is 100 square meters) of area is able to give an expected effect in the case of employing it practically, but another chemical amount containing 250g of effective ingredient, in proportion to 10 are of area is not able to wither grass weeds to death, in the other words, it cannot give a perfect herbicidal effect.

But, in the event of employing the compound of the present invention as a herbicide, a chemical amount containing 250g of effective component, as a matter of course, further a chemical amount containing 125g of less of effective ingredient, in proportion to 10 are of area, in compliance with the same treating method of conventional herbicide indicates a strong herbicidal effect and thereby a perfect prevention and extermination of weeds can be expected.

In case of foliar treatment using the compounds of the present invention, even the same amount of chemical which makes barnyard grass of grass weeds completely kill gives no damages to broadleaf plants such as radish, soy bean (Glycine max), garden pea (Pisum sativum), spinach (Spinacia oleracea) sugar beets and carrot at all, and in case of soil treatment before germination, even the same amount of chemicals which prevents large crab-grass (Digitaria adscendens) germinating gives no damages to seeds of broad leaf plants at all.

As mentioned above, a secure safety to the broadleaf crop against phytotoxicity of the herbicide is extremely high and as to its application, in the other weeds, its applicable time, its applying location and its applying concentration, it has a very broad extent and it can be used in the wider extent.

It is another advantage of the present invention that a residual toxicity in the soil or the plant and an acute toxicity for warm blooded animals and fishes are not feared because the said compounds can be employed with a low chemical concentration.

The compounds of this invention can be applied directly to the soil as pre-emergence treatment or as post-emergence treatment to plant foliage, or they can be mixed intimately with the soil, preferably post-emergence treatment to plant foliage, and may be applied to soil or plant foliar at rates of 50-1000g per 10 are, preferably 50-200g per 10 are, more preferably about 100g per 10 are.

The method of the present invention comprehends the employment of a liquid or solid composition containing one or more of the present compounds as an active ingredient.

The active ingredient of this invention may be formulated by mixing with suitable carriers in a form generally used in agricultural chemicals such as wettable powder, emulsifiable concentrate, dust formulation, granular formulation, water soluble powder and aerosol. As solid carriers, bentonite, diatomaceous earth, apatite, gypsum, talc, pyrophyllite, vermiculite, clay and others are used. As liquid carriers, kerosene, mineral oil, petroleum, solvent naphtha, benzene, xylene, cyclohexane, cyclohexanone, dimethylformamide, alcohol, acetone, and others are used. Sometimes surface active agent is added in order to give a homogeneous and stable formulation.

The compounds of this invention also can be applied admixed with other chemicals which are used in agronomic and horticultural management and are compatible with the compounds of this invention. Such chemicals can be, but are not restricted to, the classes of chemicals commonly known as plant nutrients, fertilizers, insecticides, acaricides, fungicides, herbicides and nematocides.

As for known herbicide it is recommended that the compound of the present invention is applied admixed with urea derivatives such as 3-(3,4-dichlorophenyl)-1-methoxy-1-methylurea, or N-(3,4-dichlorophenyl)N',N'-dimethylurea, triazine derivatives such as 2-chloro-4-ethylamino-6-isopropylamino-s-triazine, or 2-chloro-4,6-bis(ethylamino)-s-triazine and amide derivatives such as N-1-naphthyl-phthalamic acid.

The concentrations of the active ingredients in the herbicidal composition of this invention vary according to type of formulation, and they are, for example, used in a range of 5 - 80 weight percent, preferably 10 - 60 weight percent, in wettable powder, 5 - 70 weight percent, preferably 20 - 60 weight percent, in emulsifiable concentrates, and 0.5 - 30 weight percent, preferably 1 - 10 weight percent in dust formulation.

Thus, a wettable powder or an emulsifiable concentrate produced thereto is diluted with water to a specified concentration and thereby, it is used as a liquid suspension or a liquid emulsion for treating soils or plant foliars. Further, a dust formulation is directly used for the soil treatment or the foliar treatment.

The non-limiting examples for the herbicidal composition is illustrated as follows:

                  Example 10.                                                      ______________________________________                                          Wettable Powder     Parts by weight                                           ______________________________________                                         Compound 1          20                                                         Diatomaceous earth  37                                                         Sodium alkylsulfate  6                                                         Talc                37                                                         ______________________________________                                    

These are mixed homogeneously and reduced to fine particles. Consequently, wettable powder containing 20% of active ingredient is obtained. In practical use, it is diluted to a certain concentration with water and is sprayed as a suspension.

                  Example 11.                                                      ______________________________________                                         Emulsifiable Concentrate                                                                          Parts by weight                                             Compound 2           40                                                        Xylene               35                                                        Dimethylformamide    15                                                        Polyoxyethylene phenylether                                                                         10                                                        ______________________________________                                    

These are mixed and dissolved.

Consequently, emulsifiable concentrate containing 40% of the active ingredient is obtained. In practical use, it is diluted to certain concentration with water and then is sprayed as an emulsion.

                  Example 12.                                                      ______________________________________                                         Dust Formulation                                                                                 Parts by weight                                              Compound 3           7                                                         Talc                38                                                         Bentonite           10                                                         Clay                38                                                         Sodium alkylsulfate  7                                                         ______________________________________                                    

These are mixed homogeneously and reduced to fine particles. Fine particles is made into granules having the diameter in the range of 0.5 - 1.0mm by granulator.

Consequently, dust formulation containing 7% of the active ingredient is obtained. In practical use it is directly applied.

The superior herbicidal effect of the novel compounds of this invention is clearly illustrated by the following tests.

Test 1. Pre-emergence (soil treatment)

About 60 seeds of barnyard grass were planted in a pot having 60 square centimeters and covered slightly with soil. Said pot was kept stagnation state so as to get wet with water.

10ml of an aqueous suspension prepared by diluting an emulsifiable concentrate with water to a specified concentration was sprayed on the pot. Two weeks after spraying, the degrees of damage to the plant were observed and estimated by the value of 0 - 5 which have the following meanings:

0: no effect

1: a few slightly burnt spots

2: marked damage to leaves

3: some leaves and parts of stalks partially dead

4: plant partially destroyed

5: plant completely destroyed or no germination

The results were shown in Table 2.

                  Table 2                                                          ______________________________________                                                            Application                                                                    rate (g/10 are)                                             ______________________________________                                         Test compound No.    120    60    30  15  7.5                                  ______________________________________                                          31                  --     --    5   4   3                                     50                  --     --    5   5   5                                    107                  --     --    5   2   1                                    108                  --     --    5   3   2                                    126                  --     --    5   3   1                                    127                  --     --    5   3   2                                    128                  --     --    5   5   3                                    137                  --     --    5   3   2                                    141                  --     --    5   5   2                                    142                  --     --    5   5   3                                    143                  --     --    5   5   5                                    152                  --     --    5   4   3                                    155                  --     --    5   5   5                                    Comparative compound                                                            ##STR7##            4      2     0   0   0                                    Untreated            0                                                         ______________________________________                                    

Test 2. Post-emergence (foliar treatment)

About 50 seeds of barnyard grass were planted in a pot having 60 square centimeters and covered slightly with soil. Said pot was filled with water when the plant was grown to first leaf-stage.

An aqueous suspension prepared by diluting an emulsifiable concentrate with water to a specified concentration was sprayed on the pot. Two weeks after spraying, the degrees of damage to the test plant was observed and estimated by the value of 0 - 5 which have the same meanings as those of Test 1.

The results were shown in Table 3.

                  Table 3                                                          ______________________________________                                                             Application                                                                    rate (g/10 are)                                            ______________________________________                                         Test compound No.     125    62.5   31.3                                       ______________________________________                                          10                   5      4      3                                           18                   5      5      4                                           31                   5      5      4                                           50                   5      5      4                                          107                   5      5      4                                          108                   5      5      3                                          112                   5      4      1                                          124                   5      3      1                                          126                   5      4      3                                          127                   5      4      3                                          128                   5      4      4                                          135                   5      3      1                                          137                   5      5      4                                          141                   5      5      4                                          142                   5      5      5                                          143                   5      5      5                                          150                   5      4      3                                          152                   5      5      5                                          154                   5      4      3                                          155                   5      5      4                                          156                   5      5      4                                          Comparative compound                                                            ##STR8##             4      1      0                                           ##STR9##             3      0      0                                          Untreated             0                                                        ______________________________________                                    

Test 3. Pre-emergence

Seeds of large crab-grass was planted in a pot having 100 square centimeters. An aqueous suspension prepared by diluting an emulsifiable concentrate with water to a specified concentration was sprayed on the surface of the soil before emergence. 21 days after spraying, the degrees of damage to the test plant was observed and estimated by the value of 0 - 5 which have the same meanings as those of Test 1.

The results were shown in Table 4.

                                      Table 4                                      __________________________________________________________________________                           Application                                                                    rate (g/10 are)                                          __________________________________________________________________________     Test compound No.     300                                                                               120                                                                               60 30                                                                               15                                            __________________________________________________________________________      31                   -- 5  5  5 4                                              50                   -- 5  5  5 5                                              75                   -- 5  5  5 5                                              83                   -- 5  5  5 5                                              96                   -- 5  5  5 4                                             107                   -- 5  4  2 --                                            111                   -- 5  4  1 --                                            126                   -- 5  3  1 --                                            127                   -- 5  4  2 --                                            128                   -- 5  4  2 --                                            134                   -- 5  3  1 --                                            137                   -- 5  2  0 --                                            142                   -- 5  5  4 --                                            143                   -- 5  4  4 --                                            152                   -- 5  5  5 4                                             154                   -- 5  5  4 3                                             155                   -- 5  5  4 4                                             156                   -- 5  5  4 4                                             Comparative compound                                                            ##STR10##            4  0  0  0 0                                             Untreated                                                                      __________________________________________________________________________

Test 4. Post-emergence (foliar treatment)

Seeds of large crab-grass was planted in a pot having 100 square centimeters. An aqueous suspension prepared by diluting an emulsifiable concentrate with water to a specified concentration was sprayed on the foliar of the test plant at a rate of 100 liter per 10 are.

21 days after spraying, the degrees of damage to the test plant was observed and estimated by the value of 0 - 5 which have the same meanings as those of Test 1. The results were shown in Table 5.

                  Table 5                                                          ______________________________________                                                               Application                                                                    rate (g/10 are)                                          ______________________________________                                         Test compound No.       100    50    25                                        ______________________________________                                          10                     5      5     5                                          18                     5      5     5                                          31                     5      5     4                                          50                     5      5     5                                          75                     5      5     4                                          83                     5      5     5                                         106                     5      3     2                                         108                     5      5     4                                         125                     5      4     4                                         126                     5      5     4                                         127                     5      5     4                                         128                     5      5     4                                         134                     5      4     3                                         135                     5      4     3                                         137                     5      4     2                                         141                     5      5     4                                         142                     5      5     4                                         143                     5      5     5                                         145                     5      3     2                                         152                     5      5     5                                         154                     5      4     4                                         155                     5      5     5                                         156                     5      5     4                                         Comparative compound                                                            ##STR11##              3      2     0                                          ##STR12##              3      1     0                                         Untreated               0                                                      ______________________________________                                     

What is claimed is:
 1. A compound of the formula ##STR13## wherein R₁ is selected from the group consisting of ethyl and propyl,R₂ is selected from the group consisting of ethyl and allyl, R₃ is selected from the group consisting of methyl and ethyl.
 2. A compound according to claim 1 in which R₁ is propyl, R₂ is allyl and R₃ is methyl.
 3. The sodium, potassium, barium and calcium salts of a compound of the formula ##STR14## wherein R₁ is selected from the group consisting of ethyl and propyl,R₂ is selected from the group consisting of ethyl and allyl, R₃ is selected from the group consisting of methyl and ethyl.
 4. The sodium salt compound according to claim 3 in which R₁ is propyl, R₂ is allyl and R₃ is methyl. 